Supramolecular Liquid Crystalline Polymers

在过去的150年里，有机化学家一直关注于对共价键的理解。最近，分子识别(由弱的、非共价相互作用产生)的研究已被世界范围内公认为一个重要的智力和技术前沿。分子识别、预组织和自组织为功能超分子结构的自发生成提供了基础。现在公认的是，分子识别、定向合成和自组装是生物系统的产生和性质的主要原因。本研究的目的是利用分子识别技术自组装合成的超分子液晶聚合物，并指导其相行为。将研究两类新型聚合物：利用与烟草花叶病毒相似的原理自组装的功能性超分子聚合物，以及环状主链聚合物，以及以液晶环番(即主链液晶低聚物的环状衍生物)受体为结构单元的聚合物。第二类液晶聚合物将显示分子识别导向的相变。预计这项研究将产生分子器件，如自组装超分子合成离子通道和各种其他系统，通过与自然生物系统的类比，将选择性识别与外部调节相结合。最重要的是，这项研究将使我们能够在了解自然使用的一些过程方面领先一步，而我们对这些过程知之甚少，并将它们移植到合成超分子聚合物领域。

For the past 150 years, organic chemists were concerned with the understanding of the covalent bond. Recently, research on molecular recognition (generated by weak, non-covalent interactions) has been recognized worldwide as an important intellectual and technological frontier. Endo- (generated by convergent cavities) and exo (generated by larger bodies of similar size and shapes, or surfaces) molecular recognition, preorganization and self-organization provide the basis of spontaneous generation of functional supramolecular architectures via self-assembly from their components. It is now accepted that molecular recognition directed synthesis and self-assembly are responsible for the generation and properties of biological systems. This research aims to use molecular recognition both to self-assemble synthetic supramolecular liquid crystalline polymers and to direct their phase behavior. Two novel classes of polymers will be investigated: functional supramolecular polymers which self-assemble by using principles that resemble those of tobacco mosaic virus, and both cyclic main-chain polymers, as well as polymers containing liquid crystalline cyclophane (i.e., cyclic derivatives of main-chain liquid-crystalline oligomers) receptors as structural units. The second class of liquid-crystalline polymers will display molecular recognition directed phase transitions. It is expected that this research will produce molecular devices such as self-assembled supramolecular synthetic ion channels and various other systems which, by analogy with natural biological systems, will combine selective recognition with external regulation. Most important, this research will enable a step ahead in understanding some of the processes that nature uses and about which we know so little, and transplant them to the field of synthetic su pramolecular polymers.